CYL100 2013–14 Solved Problems in Quantum Chemistry

1. Which of the wavefunctions shown in the figure are well behaved? Give reasons for your
answer.

2. The wavefunction of a particle confined to the x axis is ψ = e− x for x > 0 and ψ = e+ x

for x < 0. Normalize this wavefunction and calculate the probability of finding the
particle between x = −1 and x = 1.

3. State, giving your reasons, which of the following functions would make satisfactory
2 2 2
wavefunctions for all values of the variable x: (i) Neax ; (ii) Ne−ax ; (iii) Ne−ax /(3 − x );
and (iv) Ne−ax , where N and a are constants.

4. Calculate the wavelength of the radiation that will be absorbed in promoting an electron
from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular
orbital (LUMO) in butadiene.

5. Calculate the energy separation between the n = 1 and n = 2 levels of a nitrogen

molecule, confined in a one-dimensional box of length 1 cm. Find the value of n that
corresponds to the average thermal energy of a nitrogen molecule at a temperature of
300 K. The average thermal energy = 12 k B T for movement in one dimension, where k B is
the Boltzmann constant. Comment on the value for n obtained.

6. For a one-dimensional gallium arsenide quantum well of width 21 nm, calculate the
difference in energies between the n = 2 and n = 3 states for travel of conduction
electrons across the width of the well. Compare your answer with the experimentally
determined value of approximately 0.05 eV.

7. For a particle moving freely along the x-axis, show that the Heisenberg uncertainty
principle can be written in the alternative form:

λ2
∆λ∆x ≥
4π
where ∆x is the uncertainty in position of the particle and ∆λ is the simultaneous
uncertainty in the de Broglie wavelength.

8. Consider a particle whose normalized wave function is

√
ψ( x ) = 2α αxe−αx x>0
=0 x<0
 (a) For what value of x does P( x ) = |ψ( x )|2 peak?
(b) Calculate h x i and h x2 i.
(c) What is the probability that the particle is found between x = 0 and x = 1/α?

9. The wavefunction of a particle moving in the x-dimension is

(
Nx ( L − x ) 0 < x < L
ψ( x ) =
0 elsewhere

(a) Normalize the wavefunction.

(b) Calculate h x i, h x2 i, ∆x.
(c) Calculate h p x i, h p2x i, ∆p x .

10. If the normalized wave function of a particle in a box is given by

(q
30
L5
x( L − x) 0 < x < L
ψ( x ) =
0 elsewhere

what is the probability of obtaining the energy of the ground state, E1 , if a measurement
of the energy is carried out?

11. Show that the function

e−iE1 t e−iE2 t
Ψ ( x, t) = ψ1 ( x ) + ψ2 ( x )
h̄ h̄
is normalized. Calculate h Ei and ∆E for this state.

12. Determine h Ei for a particle in a box with wave function

(q
30
L5
x( L − x) 0 < x < L
ψ( x ) =
0 elsewhere
CYL100 2013–14 Solved Problems in Quantum Chemistry

1. Which of the wavefunctions shown in the figure are well behaved? Give reasons for your
answer.

Answer: Only the wavefunction shown in (c) is well behaved. The one shown in (a)
tends towards infinity, and therefore violates the rule that the integral of ψ∗ ψ over
all space must be equal to one because the particle is certain to be somewhere. This
requires that the wavefunction is finite. The one shown in (b) has multiple values of
for a given value of x, and the one shown in (d) has discontinuities in the gradient,
so that dy/fdx cannot be defined at certain points.
2. The wavefunction of a particle confined to the x axis is ψ = e− x for x > 0 and ψ = e+ x
for x < 0. Normalize this wavefunction and calculate the probability of finding the
particle between x = −1 and x = 1.
Answer: Normalization refers to the requirement that
Z ∞
ψ∗ ψ dx = 1.
−in f ty

If ψ does not satisfy this property, because it is a solution to the Schrödinger

equation (SE), which is a linear equation, Nψ, where N is a constant, is also a
solution to the SE.
Ignoring the acceptability of the given function to beRa wavefunction, we proceed to
normalize the function. We look for a N, such that Nψ∗ Nψ dx = 1. That is
Z ∞ Z −∞ 
2 −x −x x x
N e e dx + e e dx = 1
0 0

Each of the integrals is a 21 so N 2 = 1 or the wavefunction is normalized.

The probability of finding the particle between x = −1 and x = 1 is obtained by
integrating ψ∗ ψ over this domain.
R1 ∗
ψ ψ dx
P = R−∞
1
∗
−∞ ψ ψ dx

In this instance, the denominator in the above expression is unity. The probability
of finding the particle in the desired region is
Z 1 Z −1 
1 2
e− x e− x dx + ex ex dx = e − e−2


P=
0 0 2
3. State, giving your reasons, which of the following functions would make satisfactory
2 2 2
wavefunctions for all values of the variable x: (i) Neax ; (ii) Ne−ax ; (iii) Ne−ax /(3 − x );
and (iv) Ne−ax , where N and a are constants.

Answer: (i) Not satisfactory; function not finite as x → ∞.

(ii) Satisfactory.
(iii) Not satisfactory; function not finite at x = 3.
(iv) Not satisfactory; function not finite as x → −∞.

4. Calculate the wavelength of the radiation that will be absorbed in promoting an electron
from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular
orbital (LUMO) in butadiene.

Answer: First, an estimate has to be made of the length of the potential well, L, in
which the π-electrons move. It seems reasonable to take the mean C-C distance
to be equal to the average of the carbon-carbon single and double bond lengths
found in a variety of non-conjugated compounds - this is a different approach from
that adopted in HW4. With d(C−C)= 154 pm and d(C−C) = 135 pm, this leads to
a value of 144.5 pm. The total length of the box is then taken to be equal to four
carbon-carbon bond lengths, giving L = 578 pm.
The highest occupied n electron state has n = 2, and the lowest unoccupied state
has n = 3. The energy required to promote an electron from one state to the other
is given by the equation:

2
32 − 22 h 2 5 × 6.626 × 10−34 J s−1


E3 − E2 = =
8mL2 8 × 9.109 × 10−31 kg × (578 × 10−12 m)2

5. Calculate the energy separation between the n = 1 and n = 2 levels of a nitrogen

molecule, confined in a one-dimensional box of length 1 cm. Find the value of n that
corresponds to the average thermal energy of a nitrogen molecule at a temperature of
300 K. The average thermal energy = 12 k B T for movement in one dimension, where k B is
the Boltzmann constant. Comment on the value for n obtained.

Answer: The energy separation between the first and second state of nitrogen molecule
(mN2 = 28 × 1.661 × 10−27 kg in a box of length 1 cm is

2
22 − 12 h2 3 × 6.626 × 10−34 J s−1


E2 − E1 = =
8mN2 L2 8 × 4.651 × 10−26 kg × (1.0 × 10−2 m)2

∆E = 3.54 × 10−38 J

The value of n that corresponds to the thermal energy at 300 K is

s
k B T 8mN2 L2
n=
2 h2
s
(1.381 × 10−23 m2 kg s−2 K−1 300 K)8(4.651 × 10−26 kg)(1.0 × 10−2 m)2
=
2(6.626 × 10−34 J s−1 )2
= 4.19 × 108

The n corresponding to thermal energy is so high that quantum effects are unlikely
to be observed.
6. For a one-dimensional gallium arsenide quantum well of width 21 nm, calculate the
difference in energies between the n = 2 and n = 3 states for travel of conduction
electrons across the width of the well. Compare your answer with the experimentally
determined value of approximately 0.05 eV.

Answer: Semiconductor quantum wells are sandwich structures made from semicon-
ducting materials. They have numerous applications in modern electronic devices.
An example is illustrated in the figure below. The base material is the III/V semi-

conductor gallium arsenide (GaAs). A thin layer of pure GaAs was been created
between two layers of aluminium gallium arsenide, a material in which some of the
gallium has been replaced with aluminium to give the formula Alx Ga1-x As. Nearly
free electrons, known as conduction electrons, can exist in these semiconductors,
and they have a much higher potential energy in Alx Ga1-x As than they do in pure
GaAs. Thus, conduction electrons in the pure GaAs become trapped between two
potential walls and behave like particles in a one-dimensional box when moving in
the x-direction, although they have complete freedom of movement in the y and z
directions. Unlike the idealized particle in an infinite potential well, this one has
finite walls. This affects the wavefunctions and energies to a small extent, but the
equations derived earlier will still give reasonably accurate values for the energies.
The existence of discrete energy levels is confirmed by the observation of selective
absorption of laser light at certain frequencies which correspond to the transition of
an electron from one energy level to another. The GaAs/Alx Ga1-x As combination
mentioned above forms the basis of the semiconductor laser used in compact
disc players. The energies are the same as that of a particle in a box, except that
the conduction electrons behave as though they have a much smaller mass than
ordinary electrons. This mass is known as the effective mass, m∗ ; for gallium
arsenide, m∗ = 0.067me .

2
32 − 22 h2 5 × 6.626 × 10−34 J s−1


E3 − E2 = =
8m∗ L2 8 × (0.067 × 9.109 × 10−31 kg) × (21 × 10−9 m)2
In eV this is 0.064 eV.

7. For a particle moving freely along the x-axis, show that the Heisenberg uncertainty
 principle can be written in the alternative form:

λ2
∆λ∆x ≥
4π
where ∆x is the uncertainty in position of the particle and ∆λ is the simultaneous
uncertainty in the de Broglie wavelength.
dp
Answer: Differentiation of the de Broglie relation, p = h/λ, gives dλ = −h/λ2 . The
uncertainty in momentum, ∆p x , can be equated with dp and the uncertainty in
wavelength, ∆λ, with − dλ (the uncertainties are positive). Thus:

∆p x h λ2
= 2 and ∆λ∆x = ∆p x ∆x
∆λ λ h
Plugging in the Heisenberg uncertainty relation yields the desired result.

8. Consider a particle whose normalized wave function is

√
ψ( x ) = 2α αxe−αx x>0
=0 x<0

(a) For what value of x does P( x ) = |ψ( x )|2 peak?

(b) Calculate h x i and h x2 i.
(c) What is the probability that the particle is found between x = 0 and x = 1/α?

dP( x
Answer: (a) The peak in P( x ) occurs when dx = 0 that is, when

d x2 e−2αx


= 2x (1 − αx )e−2αx = 0
dx
which is at x = 1/α.
(b)
Z 1/α
1 2 3! 3
Z
dx 4α3 x3 e−2αx = dyy3 e−y =


hxi = =
0 4α 0 4α 2α
Z 1/α
4! 3
h x2 i = dx 4α3 x4 e−2αx = 3 = 2


0 8α α
(c) The desired probability is
Z 1/α
1 2
Z
dx 4α3 x2 e−2αx = dyy2 e−y = 0.32


P=
0 2 0

9. The wavefunction of a particle moving in the x-dimension is

(
Nx ( L − x ) 0 < x < L
ψ( x ) =
0 elsewhere

(a) Normalize the wavefunction.

(b) Calculate h x i, h x2 i, ∆x.
(c) Calculate h p x i, h p2x i, ∆p x .
 Answer: (a)
1 1
N = qR = qR
∞ L
−∞ ψ∗ xψ dx 0
x2 ( L − x )2 dx
1 1
N = qR =q
L L5
0 ( x2 L2 − 2Lx3 + x4 ) dx 30

(b)
Z ∞ Z L
30
hxi = x |ψ|2 dx = x 5 x2 ( L − x )2 dx
−∞ 0 L
30 L
 
1 2 1 L
Z
2 3 4 5
= ( L x − 2Lx + x ) dx = 30L − + =
L5 0 4 5 6 2

Z ∞ Z L
30 2
h x2 i = x ( L − x )2 dx
x2 |ψ|2 dx = x2
−∞ 0 L5
30 L 2 4 2L2
 
1 2 1
Z
= 5 ( L x − 2Lx5 + x6 ) dx = 30L2 − + =
L 0 5 6 7 7
r
2 1
q
∆x = h x2 i − h x i = L −
7 4
(c)
Z ∞   Z L
∂ψ 30
h px i = ψ∗ −ih̄ dx = 5
x ( L − x )(−ih̄( L − 2x )) dx = 0
−∞ ∂x 0 L

Z ∞  
∗ 2 ∂ψ
h p2x i = ψ −h̄ dx
−∞ ∂x
30h̄2 L 10h̄2
Z
=− 5 x ( L − x )(−2) dx = 2
L 0 L
q √ h̄
∆p x = h p2x i − h p x i = 10
L
10. If the normalized wave function of a particle in a box is given by
(q
30
L5
x( L − x) 0 < x < L
ψ( x ) =
0 elsewhere

what is the probability of obtaining the energy of the ground state, E1 , if a measurement
of the energy is carried out?

Answer: To determine the probability, evaluate c1 :

Z ∞ Z Lr  πx  r 30
2
c1 = ψ1∗ ( x )ψ( x ) dx = sin x ( L − x ) dx
−∞ 0 L L L5
This integration is easiest performed by making a change of variables πx/L = y,
which yields √ Z √
y2
 
60 π 4 60
c1 = sin y y − dy =
π2 0 π π3
11. Show that the function
e−iE1 t e−iE2 t
Ψ ( x, t) = ψ1 ( x ) + ψ2 ( x )
h̄ h̄
is normalized. Calculate h Ei and ∆E for this state.

Answer: A measurement of the energy yields E1 , the energy of state 1, with probability
 −iE t/h̄ 2
e 1 
2
P1 = |c1 | =  √  =1
2  2

or E2 with probability
 −iE t/h̄ 2
e 2 
2
P2 = |c2 | =  √  =1
2  2
Because ∑∞ 2
n=1 | cn | = 1, Ψ ( x, t ) is properly normalized. The expectation value of
the energy in the state Ψ ( x, t) is
∞
1 1
h Ei = ∑ Pn En = 2 E1 + 2 E2
n =1

Similarly,
∞
1 1
h E2 i = ∑ Pn En2 = 2 E12 + 2 E22 .
n =1

As a result,
1
q
∆E = h E2 i − (h Ei)2 = ( E2 − E1 )
2
12. Determine h Ei for a particle in a box with wave function
(q
30
L5
x( L − x) 0 < x < L
ψ( x ) =
0 elsewhere

Answer:
Z ∞
h Ei = ψ∗ Ĥψ dx
−∞
Z ∞
!
−h̄2 ∂2 ψ30 −h̄2 L ∂2
Z
∗
= ψ dx =
x ( L − x ) ( x ( L − x )) dx
−∞ 2m ∂x2 L5 2m 0 ∂x2
30 h̄2 L 30 h̄2 3 1 1 5h̄2
Z  
= 5 x ( L − x ) dx = 5 L − =
L m 0 L m 2 3 mL2